Process for dyeing and printing with derivatives of naphthazarin.



UNITED STATES PATENT oEEIcE.

GADIENT ENGI, OF BASEL, SWITZERLAND, ASSIGNOR TO SOCIETY 'OF CHEMICAL INDUSTRY IN BASLE, OF BASEL, SWITZERLAND.

PROCESS FOR DYEING ANDPRINTIN G WITH DERIVATIVES 0F NAPI-ITHAZARIN.

Patented Oct. 31, 191

I m 1,202,821. Specification of Letters Patent. No Drawing.

To all whom it may concern Be it known that I, GADIENT ENGI, doctor of philosophy andchemist, a citizen of the Swiss Republic, and resident of .Basel, Switzerland, have invented anew and useful Process for Dyeing and Printing with Derivatives of Naphthazarin, of which the following is a full, clear, and exact specification.

It is known that naphthazarin and some of its derivatives, as for instance arylnaphthazarins, are only capable of employment for dyeing wool and printing wool and cotton either in the form of bisulfite compounds or in the form of sult'onic acids. For the dyeing of cotton these products have not. heretofore, been capable of employment. I have now found that a series of condensation and transformation products of naphthazarin and of its homologues and substitution products yield by their treatment with reducing agents leuco compounds soluble in. alkalis, having the surprising property of an affinity for textile fibers rendering them well suited for dyeing and printing the same by the methods known for the vat-dyestuffs, whereby gray, brown, brown-black, green-black, blue-black to deep-black dyeings and printings are obtained, having an excellent fastness particularly when subjected to a subsequent'treatment with metal salts.

I have ascertained that the property of dyeing textile fibers from an alkaline vat is a specific characteristic of nearly all condensation. and transformation products'of naphthazarin, this latter being itself remarkably devoid of the said property. Thus the following groups of compounds of thenaphthazarin series are, for instance, suitable for vat-dyeing.

'(a) the arylaminoderivates obtainable by the condensation of naphthazarin and of its substitution products with aromatic amins and their sulfonic or carboxylic acids.

(7)) the transformation products obtainable by heating naphthazarin, its substitution products of. the arylamino derivatcs specified under paragraph (a) in diluents or solvents with or without addition of alkal is, alkali metal sulfids alkaline earth, metal sulfids or other salts.

K Application filed .Tune 18, 1913. Serial No. 774,365.

(0) the condensation products obtainable by the action of bodies containing the group The vegetable fibers dyed according to the present process have cold sulfuric acid of 66 Be. gray-blue and hot soda-lye of 7.5 per cent. slightly green, when they are laid in the said'solvents, but do not color cold so la-lye of 2.5 per cent. andI color only by traces hot hydrochloric :ICH

The employment of the specified products.

as \'at-dycstufls for dyeing and printing will be illustrated by'the following examples:,

Example 1.

' 3 to 4 parts ofthe condensation product ofnaphthazarin and anilin obtained according to Example 2 of the German Patent No. 101,525, are transformed to a paste with 3 to 4 parts of soda lye of 30 per cent. To this paste are added 300 parts of hot water and 2 to 3 parts of sodium hydrosulfite (powder) and the mixture is heated for a short time,

whereby a brown-orange solution is pro-.

dueed. By adding hot water this solution is diluted to the desired volume and the fibers are dyed in the same at a temperature of 60 to 90 C., while common salt (30 to 40 grams the property coloring I lcnsntion in'oducts soluble in nlkalis resiiitmg from the action of other aromatic.ainins on naphthazarin accoldirna tothe' German Patent No. 101,525 can be employed forflyeing purposes. I I a @Ewamplell, i

3 parts of an arylatcd proihict insohible in nlkahs. obtained by boiling for several hours nnphtlniznrin. with alcohol in presence of anaromafic mnin, aretransformekl too rat according-to the indications of mg oxidizing djxwhpum Whitcs are obtained.

- derived froi Example I. The reslilting vntiisjndded to the dyeing bath to which 80 fgrninsof comi'non salt have been-qiiddcd ien liter and the cotton ist h'cn introduced in thehn'tln .The L said cotton is dyed for squeezed out, oxidized during 1; hour-by ex posnre to the air, rinsed and the dyeing s olev boiling[ofnnphthhzarin@withgjwater,isem of 9 d n g-"$ M;

ploycd hhlck dye lngs washing iindttolight? finally treated. for hour M90" 0., with a "L hath containing 5 grams of copper sulfate or?) gra ns of potassium chi-ornate per liter. The dyed cotton dried. l 1

When the employed condensation product insoluble in alkniis is derived from nniiin, :1 deep black is obtained, which has oniax: ccllcnt fastness to washing. light, acids and a satisfactory fastness to chlorin. By printdischarges on goods thus The corresponding condensation prodn'ct ii vpzn'nphenylenedizunin; gives a" more reddish hig -k hatingbcsides, thesam fnstness to \vnsiring,.1ight,alid' grcater fastncss tochl'orin, The condensat tion prodnctot nophthazarin with bcnziciiii furnisl iognos of :lnilin,

products obtained byboiling'in an alcoholic sion, give black vot-dyeings Thus a fast v black is for instance obtained with thecon-y densation product oiv naphthzzarin'withfspl .I'faniliic acidytlie tints of somewhat more greenish tnincdiivith the product den 1 41in. The corresponding condensation 5; mm prepared with 1 :8;naphthyiaminosuI-* 10s. a more bluish-black, while the product tierivcdffrom naphthazm'in anti orthophenyienodiiimin gives black brown \tat-dycings. The corresponding products derived from nophthazarin and the homo monoethylanilin, dimethylnnilin, naphthylmnin, diphcnylomiii; mono; mninodiphenylmnin, (iiaminodiphenylamin, nminounthriiqqinnne,' etc., give also black dycings of more greenish, more bluish or more reddish, tints than the dyeings" ob+ tamed "with; the condensation productide- Also the condensation o h v I. naphthgggrifiinth water and soda or sodium rlved from a-nilini the condensation of na inthazarin with s'ulfonic nor carboxyiic acids of aromatic amins, for. instanco iiy solution or suspeb' chin? onie' acid, or 2zfi naphthyhiminomonosuhl fOIlic acid, or nn'tiiranilic acid yielgi'isoz'ne.

is aft hl'waird, rinsed .nnd'

- f ner 1111; pp

. r i. ,i c c, in phhi znrin, with "oxyth'io [:iphthne; are nuns formed withfsoda iyem'nd liydmsulfiteim a; vat I showing-n redorange coloration. v The 1 (11, cottonflnrn is'gintrodiiced in this vat and dyed therein for half on honrfat 0;,"

tion of air, rinsed fund';eventiiallyc:-treoted finally with a"hot sorip soliition; A" beam;

A j g nsuzgii i i ns of the 'condeiisction. nc

by treatingthe 'resultingxtrfinsformitiifir 10,51;

product subsequently; with anilin" or; p'ar phenylenediaminf an; .2 transformed intp vat, which is employed ito dye, cottonizrth above syccifiemmanneti Thowdyeinm thus, afi 'r Mu e. 9? e a r-Mon c i. omm s e or ,po iiassiumlichlfomotol F, heqd tints i so; ob'tiiihedfare of e'gzcellenti'fastness A'nalogons dyoings; growtitiined wit; th condensation; pnodnct'srobta'ined by- 1 acetaji te andiby subsemfuent treatment fwith.

.ajo'innticjiinonoalorpo yiminng i 'sulfite (powder thickenin aref foregoing examples, the,

[f r-ample V l].

400 grams of alkaline thickening 100 grams of glycerin 100 grams of glucose and p 250 gransotwater are heated to 70 C. and then I 50 grams of hydrosulfitc N-F cone. are

added at 50 C.

After printing, the goods are steamed for 5 minutes in the Mather-Flatt at 100102 -(IL, and thereafter treated with a bath containing 5 grams of potassium (JlllOllliLtQPQl' liter, rinsed and soaped with boiling soapy water. i

It'awntplci 11].

' A printing color consisting of 250 grams.

oi d'yostufl' (paste), (350 grams of alkaline thickening, and 100 grams of glycerin 1s "n-inted on a .fabric- )re iared with 'lucose.

, l he 'lillHlC is then dr1ed,-steamed in moist steam Free of air in the Mather-Flatt for 3 minutes, sub ected to oxidation and subgray to black shades on textile may be employed for dyeing and printing. \Vhat I claim is: f v

1. The described process of reducing bers consisting in treating nap'hthazarin derivatives with alkaline reducing agents, applying the leuco compound thus produced on I the fibers and finally oxidizing the same on the fibers.

2. The described process of producing g-ray to black shades on the textile fibers consisting in treating naphthazarin derivatives with alkaline reducing agents, appI-yin .the leuco-compound thus produced on the hers, oxidizing the same on the fibers and finally sequent treatment with pptassium chromate' or copper sulfate. In'an analogous manner all compounds of the 'naphthazarin series above specified treating the dyed material with hot solutions of metal salts operable to impart fastness to I the shade produced. a

3. As a new article of manufacture, va, textile fiber dyed with the oxidation of a leucocompound of na-phthazarln-derivatives, the dyed fiber coloring cold sulfuric acid of GG B. gray-blue, hot hydrochloric acid of 21- Be. only by traces and hot soda.

80 roducts lye of 7 .5 per cent. slightly green, but not coloring cold soda lye of 'Z .5 per cent.

In witness whereof I have hereunto signed my name. this 4th day of June, 191-3; in the I presence of two subscribing witnesses.

- GADIENT ENGI. I

Witnesses: v

GEO. Girronn, AMAND Rri'mn. 

